Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes

doi:10.1016/S1872-2067(21)63809-3

Abstract

Abstract:

The discovery of the high activity and selectivity of boron-based catalysts for oxidative dehydrogenation (ODH) of alkanes to olefins has attracted significant attention in the exploration of a new method for the synthesis of highly active and selective catalysts. Herein, we describe the synthesis of porous boron-doped silica nanofibers (PBSNs) 100-150 nm in diameter by electrospinning and the study of their catalytic performance. The electrospinning synthesis of the catalyst ensures the uniform dispersion and stability of the boron species on the open silica fiber framework. The one-dimensional nanofibers with open pore structures not only prevented diffusion limitation but also guaranteed high catalytic activity at high weight hourly space velocity (WHSV) in the ODH of alkanes. Compared to other supported boron oxide catalysts, PBSN catalysts showed higher olefin selectivity and stability. The presence of Si-OH groups in silica-supported boron catalysts may cause low propylene selectivity during the ODH of propane. When the ODH conversion of ethane reached 44.3%, the selectivity and productivity of ethylene were 84% and 44.2% g_cat^-1 s^-1, respectively. In the case of propane ODH, the conversion, selectivity of olefins, and productivity of propylene are 19.2%, 90%, and 76.6 μmol g_cat^-1 s^-1, respectively. No significant variations in the conversion and product selectivity occurred during 20 h of operation at a high WHSV of 84.6 h^-1. Transient analysis and kinetic experiments indicated that the activation of O₂ was influenced by alkanes during the ODH reaction.

Key words: Electrospinning, Nanofibers, Boron-based catalyst, Oxidative dehydrogenation, Light alkanes

Bing Yan, Wen-Duo Lu, Jian Sheng, Wen-Cui Li, Ding Ding, An-Hui Lu. Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes[J]. Chinese Journal of Catalysis, 2021, 42(10): 1782-1789.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63809-3

https://www.cjcatal.com/EN/Y2021/V42/I10/1782

Figures/Tables 9

Fig. 1. SEM images (a,b), TEM image (c), and STEM-EDX mapping (d) of PBSN-3 catalyst.

Fig. 2. Structural characterization of the PBSN catalysts. (a) N2 sorption isotherms (curves for PBSN-1 and PBSN-2 were vertically shifted respectively by 70 and 30 cm3 g-1); (b) pore size distributions; (c) XRD patterns; (d) FTIR spectra.

Fig. 3. ODH of light alkanes over the PBSN-3 catalyst. (a) Dependence of ethane conversion and product selectivity on reaction temperature; (b) stability test of ethane over PBSN-3 and B2O3/gel catalysts at similar initial conversion rates; (c) dependence of propane conversion and product selectivity on reaction temperature; (d) stability test of propane at 545 °C; gas feed, 16.7 vol% C2H6, 25 vol% O2, and N2 balance; WHSV of C2H6, 12.8 h-1; 25 vol% C3H8, 25 vol% O2, and N2 balance; WHSV of C3H8, 84.6 h-1.

Fig. 4. Dependence of propylene selectivity on propane conversion over PBSN-3 and B2O3/gel catalysts. Reaction conditions: 25 vol% C3H8, 25 vol% O2, and N2 balance; 520 °C, WHSV of C3H8, 16.9-169.2 h-1.

Fig. 5. SEM (a,b) and TEM (c,d) images of spent PBSN-3 catalyst.

Table 1 Elemental analysis results of PBSN-3 from XPS.

Catalyst	Elemental composition (at%)
Catalyst	B	Si	O
Fresh	3.0	36.5	60.5
Spent	2.9	37.9	59.2

Fig. 6. 11B MAS NMR spectra with a 14.1 T magnet of fresh (a) and spent (b) PBSN-3 catalysts.

Fig. 7. Mass spectra of H2O and C2H4 species upon pulsing (a) C2H6 and (b) C2H6/O2 onto the PBSN-3 catalyst at 600 °C.

Fig. 8. Effect of the partial pressure of light alkanes and oxygen on alkanes consumption rate in the ODH reaction (a and b for ethane, c, and d for propane) over the PBSN-3 catalyst. Reaction conditions: gas feed, (a) 0.7 vol%-12.6 vol% C2H6 and 25 vol% O2, (b) 4.6 vol%-14.1 vol% O2 and 16.7 vol% C2H6, (c) 1.8 vol%-16.7 vol% C3H8 and 25 vol% O2, (d) 1.8 vol%-16.7 vol% O2 and 25 vol% C3H8, and N2 balance; temperature, (a,b) 540 °C and (c,d) 590 °C.

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